Process for dyeing acid-modified polyester fibers and novel thiazoleazo-type cationic dyes

ABSTRACT

A process for dyeing acid-modified polyester fibers comprising contacting the fibers with a dye bath containing a thiazoleazotype cationic dye of the formula (I);   wherein R1 and R3 are each a C1 - C2 alkyl group, R2 is a hydrogen atom, a C1 - C2 alkyl group or a C1 - C2 alkoxy group, R4 is a hydrogen atom or a C1 - C2 alkyl group, R5 is a hydroxyl group or a C1 - C2 alkoxy group, and X is an anion. The dye compounds of the formula (I) dye acid-modified polyester fibers a bright shade and with good light fastness. The dye compounds of the Formula (I) wherein R2 is a hydrogen atom or a methoxy or ethoxy group are novel dye compounds.

United States Patent 1 1 in] 3,874,847

Ohkawa et al. Apr. 1, 1975 PROCESS FOR DYEING ACID-MODIFIED [56] References Cited POLYESTER FIBERS AND NOVEL UNITED STATES PATENTS THIAZOLEAZO-TYPE CATIONIQ DYES 3.504.997 4/1970 Clapham 8/21 R [75] Inventors: Masaaki Ohkawa, Takatauki;

Seizo Konishi, Minoo; Sadaharu Abeta, Toyonaka; Tetuo Okaniwa, Minoo; all of Primary Examiner-Donald Levy Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn & Macpeak Osaka, Japan [57] ABSTRACT [73] A i S i Ch i l C A process for dyeing acid-modified polyester fibers Limited, Osaka, Japan comprising contacting the fibers with a dye bath containing a thiazoleazo-type cationic dye of the formula O l S R I N N N 3 I l X Ch CH-R R 1 1 CH CH OH 2 R: J J

[22] Filed: Aug. 21, 1973 wherein R, and R are each a C C alkyl group, R

is a hydrogen atom, a C C alkyl group or a C C alkoxy group, R is a hydrogen atom or a C C alkyl group, R is a hydroxyl group or a C C alkoxy 211 Appl. No.: 390,265

[30] Foreign Application Priority Data group, and X is an union. The dye compounds of the Aug. 30. 1972 Japan 47-86996 formula y acid-modified Polyester fibers 11 bright May 31,1973 Japan 48-61530 shade and with good light fastness- The dye May 31, 1973 Japan 48-61531 PoundS 0f the Formula wherein is 11 hy atom or a methoxy or ethoxy group are novel dye [52] U.S. Cl 8/41 C, 8/168, 260/158 compounds- [51] Int. Cl D06p 3/76 [58] Field of Search 8/168, 41 C 8 Claims, No Drawings PROCESS FOR DYEING ACID-MODIFIED POLYESTER FIBERS AND NOVEL THIAZOLEAZO-TYPE CATIONIC DYES BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing acid-modified polyester fibers with a cationic dye bath containing new dye compounds, and more particularly, to a method for dyeing acid-modified polyester fibers with a specific thiazoleazo cationic dye.

2. Description of the Prior Art Of the various synthetic fibers available, the demand for polyester fibers increases every year due to the superior properties of polyester as a fiber. The fiber is rendered dyeable with a cationic dye by modifying the fiber with acidic substances, as disclosed in, for example, Japanese Patent Publication No. 10497/59. Acid modified polyester fibers, as disclosed hereinbefore and in US. Pat. No. 3,018,272 are well known. Cationic dyes for acid-modified polyester fibers should have the following superior properties to those of conventional cationic dyes:

i. higher fastness to light on the acid-modified polyester fiber,

ii. less decomposition during a high temperature dyeing,

iii. good compatibility with other dyes of different shade (the same dyeing rate), and

iv. less staining of or less decomposition due to other fibers such as wool or regular polyester fibers frequently used in blends with acid-modified polyester fibers.

As disclosed in German Offenlegungsschrift 2,129,271 and Belgian Patent 728,033, it is well known that thiazoleazo-type cationic dyes can be applied on acid-modified polyester fibers.' On the other hand, it is also well known that dyes having a structure similar to the present dyes can be advantageously applied on acrylic fibers. as disclosed in Japanese Patent Publicaeffects of these fibers used in the blends on the cationic dyes during dyeing cannot be ignored. For example, the dyes are sometimes decomposed by a reductive group present in the blend fibers.

The inventors have studied the dyeing of acidmodified polyester fibers using thiaZoleazo-type blue dyes, and have found that the blue dyes were exhausted so much faster than the other cationic dyes of different shades that level dyeings did not result and these dyes were not suitable for a combination dyeing. In addition, it was found that the same phenomenon was also observed when these dyes were applied to acrylic fibers in trichromatic dyeing as one of the three primary colors compatible with one another.

In addition, the inventors found that dyeings of lower fastness to light on the fiber than on acrylic fiber resulted. These factors are. of course, completely due to the differences between acrylic fiber and acid-modified polyester fiber as can be-understood from the comparative data shown in Table I hereinafter.

It is clear from the above that the conventionally employed thiazoleazo-type blue dyes cannot be used satisfactorily as a dye for acid-modified polyester fibers. The inventors studied general purpose thiazoleazo-type blue dyes for use with acid-modified polyester fibers and completed the present invention.

SUMMARY OF THE INVENTION It is generally well known that thiazoleazo-type cationic dyes are used for dyeing acid-modified polyester fiber, however, their fastness and dyeing properties are not satisfactory. As a result of a study on new thiazoleazo-type blue dyes for acid-modified polyester fiber having desirable fastness and dyeing properties, the inventors found that the specific dye compounds of the Formula (1) below have very good properties and can be used in a dyeing process'for acid-modified polyester fibers.

The thiazoleazo-type cationic dyes of this invention used in the dyeing process of this invention for acidtion No. 15791/71, Netherlands Specification modified polyester fibers are represented by the follow- 6,608,698 and British Patent 787,369 in addition to the ing Formula (1) N N, N X N CH CH-R l CH CH OH 5 above two patents. However, these dyes useful for dyeing acrylic fibers are not necessarily useful for dyeing acid-modified polyester fiber, because the dyes, particularly the blue dyes thereof, give dyeings of lower fastness to light on the fiber than on acrylic fiber, and, moreover, the dyes should be applied on the fiber, by a high temperature dyeing (1l0-13()C) or a carrier dyeing, under more severe conditions than used with acrylic fiber at 90 to 100C.

It is necessary, therefore, for the dyes to have higher fastness to light and higher stability to high temperature than required for acrylic fiber in order to apply on acidrnodified polyester fiber.

The acid-modified polyester fiber is more frequently used in blends with other fibers such as wool, other types of polyester or cellulose than is acrylic fiber, and

The most important structure features of the dye compounds of the Formula (I) of the present invention are that the nitrogen atom constituting the thiazole nucleus is quarternized with a hydroxyethyl group and that the R substituent is a hydroxy group or a methoxy or ethoxy group, however, they can display their fuctions to'the utmost even when they have the structure of the Formula (I) as a whole. The dye compounds can be prepared by well-known methods, for example, by R diazotizing Z-amino-benzthiazole in an acid medium, N coupling the reaction product with aniline derivatives, CH CH 'R I and then quarternizing the resultant azo compounds 2 4 with ethylene oxide in an acid medium. 2 R

The present dye compounds give dyeings of a bright 5 blue shade, have high heat stability thus permitting wherein R is a hydrogen atom, a methyl. ethyl, meth their use in hot water and high fastness to light on the oxy or ethoxy group. R is a methyl or ethyl group,,R fiber. and have quite an appropriate dyeing rate (comis a hydrogen atom, a methyl or ethyl group, and R -,1 is patibility) with other dyes normally used for dyeing IO a hydroxyl. methoxy or ethoxy group, reacting the reacid-modified polyester fibers. Furthermore, they stain sultant compounds of the Formula (lV),

l S R N CH CH-R other fibers which may be present in a dyeing bath less, wherein R R R R and R,-, are each as defined and they are very stable to reductive fibers such as above, with ethylene oxide in the presence of acid ina wool. Therefore, the present dye compounds have adsolvent, and then salting out of the product. vantages that they can give level and bright dyeings on The compounds of the Formula (ll) include 6- acid-modified polyester fiber on dyeing of blends of the methoxy-2-aminobenzthiazole, and 6-ethoxy-2- fiber with a reductive fiber. aminobenzthiazole. The process conditions and the like Moreover, the present dye compounds can advantaare disclosed. in German Offenlegungsschrift geously be used not only alone or in combination, byt 2,129,271. also for dyeing acid-modified polyester fiber alone or The compounds of the Formula (Ill) include blends of the fiber, such as wool blends. The dye com- N,N-ethyl-B-oxyethylaniline, N,N-ethylB- pounds can be said to be very valuable dyes having a oxypropylaniline, N,N-ethyl-,B-oxy-n-butylaniline, wide range of application. N,N-methyl-B-oxyethylaniline, N,N-methyl-,8-

However, they are not as useful for dyeing polyacryloxypropylaniline, N,N-methyl-B-oxy-n-butylaniline, onitrile fiber, because they have a much too slow dye N,N-ethyl-B-oxyethyl-m-toluidine, N,N-ethyl-B- ing rate to be compatible with other dyes used in a oxypropyl-m-toluidine, N,N-ethyl-B-oxy-n-butyl-mcombination dyeing with aerylonitrile fibers. toluidine, N,N-methyl-,8-oxyethyl-m-toluidine, N,N-

As described above, the present invention also remethyl-B-oxypropyl-m-toluidine,N,N-methyl-B-0xybulates to a process for dyeing acid-modified polyester tyl-m-toluidine, N,N-methyl-B-oxyethyl-mfiber with dyes of the Formula (I). Polyester fiber is ethylaniline, N,N-ethtyl-B-oxyethyl-m-ethylaniline, N,-

rendered dyeable with cationic dyes by modifying the N-methyl-B-oxyethyl-m-phenetidine, N,N-ethyl-B- fiber with acidic substances. Such fibers whiehare oxyethyl-m-phenetidine, N,Nmethyl-B-oxypropyl-mmodified with acidic substances are well known and are 4( phenetidine, N,N-ethyl-B-methoxyethylaniline, N,N-

commercially available as Dacron T-64, (designated in ethyl-,B-methoxypropylaniline, N,N-ethyl-B-methoXy-' US. Pat. No. 3,357,782, col. 3, line 40 et seq. as the ren-butylaniline, N,N-methyl-B-methoxyethylaniline, N,-

action product of polyester and sulfoxisophthalic acid) N-methyl-B-methoxypropylaniline, N,N-methyl-B-. Dacron T-65 and Dacron T-92 (trade mark, produced butylaniline, N,N-methyl-B-ethoxyethylaniline, N,N-,

by the E. l. du Pont de Nemours, Co., inc). methyl-B-ethoxypropylaniline, N,N-methyl-B-ethoxy- Among the present dyes of the Formula (I), the dyes n-butylaniline, N,l\l-ethyl-B-eth0xyethylaniline, N,N-. of the Formula (I); ethyl-B-ethoxypropylaniline, N,N-ethyl-B-methoxyethf i N CH CHR X CH CH OH 2 R wherein R R,,, R R and X are each as defined yl-m-toluidine, N,N-methyl-,G-methoxyethyl-mabove, and R is a hydrogen atom, methoxy or ethoxy toluidine, N,N-methyl-B-ethoxyethyl-m-toluicline, N,N- group. are new dyes. methyl-B-ethoxyethyl-m-toluidine, N,N-methyl-B- The two dye compounds (I) and (I) can be prepared methoxyethyl-m-phenetidine, N,N-ethyl-,B- by diazotizing a Z-aminobenzthiazole of the Formula methoxyethyl-m-phenetidine, N,N-methylB.-. (ll), methoxyethyl-m-methylaniline, N,N-methyl-fi-. ethoxyethyl-m-ethylaniline, N,N-ethyl-Bmethoi yeth-. 1 S yl-m-ethylaniline, N,N-ethyl-B-ethoxyethyl-m- NH (II) ethylaniline. N,N-methyl-fi methoxyethyl-m-anisidine., 2 N,N-ethyl-,B-methoxyethyl-m-anisidine, N,N-methyl-B.-

oxyethyl-m-anisidine, N,N-ethyl-fi-oxyethyl-manisidine, N,N-methyl-B-ethoxyethyl-m-anisidine, and wherein R, is a methyl or ethyl group, using conven- N,N-ethyl-B-ethoxyethyl-m-anisidine. tional techniques, reacting the resultant diazo com- Specific examples of the dyes of the Formula (I) are t pound with anilines of the Formula (Ill), set forth below:

Among the present dyes of the Formula (I), the dyes wherein R and R,, are each an ethyl group, R is a hydrogen atom, R is a hydrogen atom or methyl group, and R is a hydroxyl group or a methoxy group, are especially preferred because of economic reasons, heat stability and dyeing rate.

Suitable examples of the anion, X, are chlorine ion, bromine ion, iodine ion, hydroxyl ion, carbonate ion, bicarbonate ion, sulfate ion, bisulfate ion, perchlorate ion, phosphate ion, phosphomolybdate ion, phosphotungstate molybdate ion, oxalate ion, acetate ion, maleate ion, propionate ion, benzenesulfonate ion or a complex ion such as, e.g., ZnCLf. A chlorine ion or ZnCL, is preferred.

Acid-modified polyester fibers can be dyed with the I present dyes, using the conventional process, at a bath temperature of 1 10 to 130C in a dyeing bath containing the present dyes of 0.1 to '7! o.w.f. 1n the process, it is preferred to adjust the pH ofthe dyeing bath to 3.5 to 5.0 with a buffer such as a sodium acetate-acetic acid buffer, a sodium phosphate-phosphoric acid buffer, etc., and in some cases Gaubcr's salt may be added to the dyeing bath to maintain the stability of fiber.

A small amount of cationic-type retarder such as derivatives of higher fattey acids having from about to carbon atoms may be added to reduce the rate of dyeing, where desired. The present dyes can be applied to carrier dyeing. Carrier dyeing is a well-known technique, for example, as disclosed in British Patent No. 1,192,168. lt-is preferred, in this case, that the carrier be present at a level of 5 to percent o.w.f., the bath temperature be 90 to 1 10C and the pH ofthe bath be 3.5 to 5.0. Preferred carriers are nonionic type carriers such as the biphenyl type nonionic carrier commercially available as Calorid ELF-C, produced by Tanatex C 0., Ltd.

CH CH o 3 3 5 1 N N N\ N CH2(IJHC2H5 01 (1-17) 1 CH OH CHZCHZOH 611 0 s N C2H5 N N 01' (I 18) N CHZC1IHCH3 1 CH OH CH2CH2OH 3 CH 0 c H I CHZCIIHCHB (L19) OCH I CHZCHZOH 3 0 11 0 s FX 0 a,

N N\ \1;I 0C; CHZCIIHCH3 (L20) The present dyes can advantageously be applied, in the form of a higher aliphatic acid salt thereof. for example, the alkali metal salts, e.g., the sodium and potassium salts of higher aliphatic carboxylic acids having about 10 to 15 carbon atoms, to a solvent dyeing process for the fiber together with a small amount of water (e.g., 40-100 percent o.w.f.) and halogenated hydrocarbon, for example, trichloroethylene, tetrachloroethylene, etc.

The present invention will be illustrated more specifically by reference to the following examples which are only given for the purposes of illustration and are not to be interpreted as limiting. 1n the examples, all parts and percents are by weight.

EXAMPLE 1 To 44.4 parts of a compound of the formula,

CHO

, K W Q C H O The concentrated cationic dye, thus obtained, was and a well-known red dye (E) of the following formula diluted with sodium sulfate, sodium chloride and dextrin at a level of about 4 times by weight so as to equal 3 the strength of a commercially available cationic dye. I N N 0.2 parts of the dye was dissolved in 500 parts of water,

and the solution was adjusted to a pH of 4 to 5 with an I acetic acid-sodium acetate buffer to prepare a dyeing CH CHCH bath. parts of Dacron T-92 (modified polyester fi- 5 ber, trade mark of du Pont, dyeable with cationic dye) was introduced therein and dyed at 120C for 40 min- 11 As shown in Table the y g y g of u Three dyeing baths (bath ratio 1 50) were prepared bright blue shade and good light fastncss on Dacron whi h consisted of 0.1 part of the dye of the Formula T-92, and also gave little staining on wool and Tctoron,

a regular polyester by Toray Industries, lnc. and Teijin Ltd.

The present dye showed high stability to hot water required on a high temperature dyeing of modified polyester fiber. Furthermore, it was found from the following test that the dye showed higher level property than well-known conventional dyes (A), (B) and (C).

acid-sodium acetate buffer for adjusting the pH of the each of the dyeing baths which was then heated, at a respectively. The dyed materials were removed from the baths when the temperature reached 100C for one bath, 105C for another bath, and for the last bath after ca 0 a BI'ltlzh Patent 3 S C2115 8 7 7 5 9 N N Q 1 on L 5 British Patent CH3O s (32H 787.3 9 U -N=N N/ 5 Japanese Patent CHEO C H Publication No. S 2 5 79 /7 N N N/ CH CH OH and good compatibility with a well-known yellow dye 40 minutes at. 120C. Then new samples of Dacron (D), Sumiacryl (ioldcn Yellow N-GL (C.I. Basic Ycl- "1 92 were introduced into the residual baths and dyed. low 28, a product ofSumitomo Chemical Co., Ltd., Ja Good results were obtained. that isia comparison bepan) (L1), 0.1 part of Cl. Basic Yellow 28, and an acetic baths to 4. 10 parts of Dacron T-92 was introduced into rate of lC/min., from to C, and C,

tween the green shades of the first samples dyed and i l3 14 second samples dyed at each dyeing temperature continued at 30 to 40C for about 4 hours. The reacshowed that the difference between the two was not a tion mixture was discharged into 1200 parts of water. difference in shade but in depth. treated with activated carbon and salted out with 200 However. when the same procedure was carried out parts of sodium chloride. A cationic dye of the formula except that the well-known blue dye (A). (B) or (C) 5 was obtained.

CHZCHZOH J was used instead of the blue dye of the Formula (l-l The concentrated cationic dye thus obtained was dia large change in the shade was observed such as a Is luted with a suitable diluent to equal the strength of a more yellowish shade with the shorter period of dyeing commercially available cationic dye.

and a more bluish shade with the longer period of dye- 0.2 parts of the dye was dissolved in 500 parts of waing. ter, and the solution was adjusted to a pH of 4 to with EXAMPLE 2 an acetic acid-sodium acetate buffer to make a dyeing bath. 10 parts of Dacron T-65 (trade mark. a modified A dye of the following Formula polyester fiber dyeable with cationic dyes. a product of N cn cncn 01 (1-4) I l ca ca on I OH gave dyeings of a bright blue shade and good light fastdu Pont) was introduced therein. and dyed at 120C for ness on polyacrylonitrile fibers. The dye. prepared in minutes. As shown in Table l. the dye gave dyeings the same way as described in EXAMPLE Lgave bright of a bright greenish blue shade on Dacron T-65 having blue dyeings on Dacron T-92 having higher fastness to W good light fastness and stability to hot water. Furtherlight and higher stability to hot water than those of U more, the dye was stable to reductive fibers Such as well-known dyes. The dye also showed good compatiwool, nd gave bright and level dyeings on a blend of bility with other dyes, e.g., the yellow and red dyes de- Dacron "[165 i h h reductive fib scribed in Example I and little staining on other fibers using the same test as described in Example 1. The re- 40 EXAMPLE 4 sults o tain d 11 Show" in Table 1 0.2 parts of a dye of the following formula,

g s x N N N" \N C H OH 01 (L3) CH CH OH The dyeing properties of the present dyes which were was dissolved in 500 parts of water and the solution was dyed in the same way as described in Example I are as adjusted to a pH of 4 to 5 with an acetic acid-sodium shown in Table 2. acetate buffer. 10 arts of Dacron T-64 (trade mark of modified polyester fiber dyeable with cationic dyes EXAMPLE 3 produced by du Pont) was introduced therein and dyed at l20C for 40 minutes. The dye gave bright blue and To 46.] parts of a compound of the formula. level dyeings on Dacron T-(14 having good light fastness were added 45.0 parts of glacial acetic acid and 33.4 and little staining on weal and Tetoron. as shown in parts of percent formic acid, and the mixture was Table l.

heated to 40 to 50C while stirring. 37.0 parts of ethyl- The dye also showed very gnarl stability to hot water ene oxide was passed therethrough slowly at the same as required on a high temperature tlyeing of modified temperature, and thereafter the reaction was furthtl polyester fiber EXAMPLE 5 A dye of the following formula (EH30 C S H l N -N N/ 2 5 T \t N m (,H c;HH 61 (1-19) I k CHZCHZOH cH o C H l N N N N 2 3 c1- (1-18) CH OH CHZCHZOH 3 1 than those of the well-known dyes, as shown in Table l were obtained.

The dyeing properties of the present dyes which were dyed in the same way as described in Example I are as shown in Table 3.

Table 1 Dyeing Properties of 16 HEXAMPLEQ gave bright blue dyeings on polyaerylonitrile fiber hav ing good light iastness. When the dye was applied to dyeing of Dacron T-64 in the same way as described in I Example I, it gave bright blue dycings thereon having higher fastness to light and higher stability to hot water than those of the well-known dyes as shown in Table l The dye also showed good compatibility with other I dyes and little staining on other fibers in the same test as described in Example l.

The dyeing properties of the present dyes which were dyed in the same way as described in Example I are as shown in Table 4.

the Present: Dyes Stability to Ref Light 5 Dye Structural Formula Water Fastness' 1ooc x 120c x 40 min. 40 min.

c H y (1-1) S Z@ FN=N-QN 2 5 Present Invention N c H OH Znc13 95 90 5 (Example l) (g 2 4 i HZCHZOH s y a c o c a Present Invention 5 2 2 5 cl 95 92 5 (Example 3) I C H OCH CHZCHZOH y -3) H c o Present Invention 5 2 (1 N: N N: 2 5 (Example 4) N I CH 0 11 0 c1 98 95 5 cu cu os 3 TH C 0 S 5 2 C H Ger. Offen. @Q 5 2,129,271 v 2 C1 90 4 5 CH g:C H

'H C O s 5 2 c a Ger. Offen. 2 5 2,129,271 C H 0CH I I CHZCFFC H v 60 4 5 Table l (cont'd) Stability to Ho t) Water Light- 2) Oc t Dye Structural Formula 28 23 Fas Hess H C O. S C H Ger. Offen. (1 N= Q- N 95 an 4 5 2,129,271 I 0 11 011 cn cn-c n a k 611 e H C O C H 7 Ger. Offen. 5 2 }N wQ-u 5 90 60 4 5 2,129,271 I 0 11 011 CH CHCH OCH 6H Belgian 5 2 S c 11 01 Patent y N-N N\ 24 728,033 I? C H Cl C1 4 CH CH OH Netherlands S Z 2 5 Specification 1 H 0H 01 90 4 6,608,698 2 4 Note:

1) The ratio of the absorbances at h determined before and after the treatment.

2) Rated according to JIS L 0841.'

Table 2 Dyeing Properties of the Present Dyes Lightstability 5 Staining Dye Structural Formula fastness Hot water Medi- Medi- Teto- Deep Deep 001 um um l'On 2 Q British N N i t Patent NI Z Z Cl 4 5 4 5 90 3 4 3 4 (B) r C11 0 S C H Convent- British -N=N-u c1 4-5 4-5 00 90 3-4- 3-4 ional Patent 1* v C H Dyes 787,369 CH CH O S /C H J 225115222 3 SU c1 so 55 15791/71 I 2 5 CH CH OH C H O S C H F KM QW (Example 1) a Z A zncl -5 5 9o 93 4-5 5 Present Z Z Dyes r I Dye (1-4) 3 5 z s (Example 2) N- N N\ 9 Cl 4-5 5 92 92 4-5 5 CH cu OH- OH 3,874,847 a I 19 I 20 5 Table 2 (Cont'd) Ligm? Stability 2;: staining) 5 fastness Hot Water 7 Dye Structural Formula Medi Medi Tetoum Deep I um Deep Wool CH O S C H De(I-5) y CH HC H c1 4-5 5 93 93 4-5 5 OH 5 Present Z Z Dyes 0 n 0 s- ,c H Dye (b7) 2 5 (I N=N N 2 5 Cl 4 5 5 93 93 4 5 5 bf CH CHCH V 6a CH CH OH Note:

1) Rated according to .118 L 0841.

2) Testing was carried out by heating two solutions at 120C for 4Q minutes, I

one containing 0.02 g/l and the other containing 0.2 g/l of dye, respectively.

The figures are the ratio in percent of the absorbance at I X of the heated dye to the unheated dye.

3) Rated with aid of the Gray Scale for the change in'stain according to .118 L 0805.

Table 3 Dyeing Properties of the Present Dyes Light- Stability o 3)v Fastness Hot Waterstaining Dye Structural Formula Hedi Deep Medi Deep Wool Teto um um ron (A) on o s} c n v 3 2 5 British (1 N WQ Patent i C H OCH Cl 4 5 4 5 90 90 3 4 3 ,4 v Convent- 787369 CH ional y y Dyes (B) CH 5 0 1-1 Ger. Offen. 'N =N"N 4-5 5 75 75 4 5 5 2,129,271 I C H OCH W 5 CH CHCH 2 3 z I f H s y (1-2) 2 5n N m0 K 2 5 71 4-5 5 9o 93 4- 5' (Example 3 f H OCH y 5 CH CH OH "tn 0 s I c H ye Q) N 4-5 5 92 92 4-5 5 Present l 5 CH CHCH Cl Dyes 8 2 3 I CH CH OH 3 4 "ca 0 s c H Dye (I 9) 3 @J 25 CH QHC H Cl 4-5 5 93 93 4-5 5 5 T ocn CH CH OH 3 Table 3 (Cont'd) Light- Stability o 3) fastness Hot Water Stalning Dye Structural Formula fii Deep gi Deep Wool Teggfi CH O S ,CH

3 3 Dye (I-lO) Q =N Q CH OCH CH CH OH 3 L C H O S N :N N C H Dye (1-11) CH HCH Cl 4-5 5 93 93 4-5 5 CH CH CH OH L C H O S. CH F2 5 3 Present Dye (I 12) (I 4-5 5 92 95 4-5 5 Dyes cu cm on 3 C H F cu s 2 5 Dye (1-13) m N: Q R

I C I-I OCH C1 4-5 5 95 97 4-5 5 CH CH CH OH 3 cn o s N m N N,cn

Dye (1-14) Q C H De H cl 4 5 5 95 96 4 5 5 1 CH 2 4 2 5 CH CH OH "ca 0 s c H Dye (1-15) N=N'-N 25 1 C H OCH C1 4-5 5 97 97 4-5 5 OCH 2 4 3 CH CH OH 3 C H O S/ N: N N CH Dye (1-16) (I Z 4-5 5 95 95 4-5 5 CH CH OH Note:

1), 2), 3): See Table 2.

Table 4 Dyeing Properties of the Present Dyes Light- Stability o 3) fastness Hot Water Stalning Dye Structural Formula Medi Med1 Tet? Deep Deep Wool ron um um C H O S N =N N I C H Dye (1-3) C H OH 4-5 5 95 98 4-5 5 H 2 4 (Example 4) CH CH CH 3 Dye (1-6) z s fl n NQ N( 2 5 CH HCH CH 23 4-5 5 95 98 4-5 5 cu cn on I CH3O CH3 Present Dye (1-17) (I N =N Q1! 4-5 5 93 93 4-5 5 Dyes CH HC H CH3 23 2 cu cn on Cr C H O S wherein R is a one to two carbon atoms alkyl group, 45 6. The process according to claim 4, whcrein said R is a hydrogen atom, a one to two carbon atoms alkyl is a hydroxyl group or a one to two carbon atoms alkoxy group, and X- is an anion.

2. The process according to claim 1, wherein said dye bath is at a temperature of from I 10 to l30C.

Table 4(Cont'd) Light 1 Stability o 3) fastness Hot: We ter stalm'ng Dye Structural Formula Medi- D e Medi- Dee wool Tetourn e p um P [011 "cs 0 s ,c H I Dye ms 3 U N: N-N' 5 4-5 5 96 96 4-5 s N ca CHCH c1 (Example 6) 1 CH 26H 3 cu cu OH Present 2 2 Dyes c H 0 s H Dye (PM 2 5 U N 2 5 I *1 CH CHZSHCH Cl 4-5 5 95 95 4-5' 5 3 a 1 Ga er-1 01i Note: 1) 2) 3) See Table 2.

While the invention has been described in detail and 3. The process according to claim 1, wherein the dyewith reference to specific embodiments thereof, it will ing is carried out in a dye bath additionally containing be apparent to one skilled in the art that various a non-ionic type carrier. changes and modifications can be made therein with- 4. The process according to claim 1, wherein in said out departing from the spirit and scope thereof. compound of the Formula (I) R is an ethyl group, R

What we claim is: K is a hydrogen atom or a methyl group, R is ancthyl LA process for dyeing acid-modified polyesterfibers group R i a h drogen atom and R is a hydroxyl with a cationic dye, comprising contacting said polyesgroup or a methoxy group. i ter fibers with a dye bath containing a cationic dye 5. The process according to claim 4, whereinsaid compound of the Formula (I), compound of the formula (I) is R 0 compound of the Formula (I) is,

S C H 1/ 2 5 N =N N\ N (111 011 011v X? g CH3 CH CH OH 7. The process according to claim 4, wherein said compound of the Formula (I) is,

CH2CH2OH according to claim l. 

1. A PROCESS FOR DYEING ACID-MODIFIED POLYESTER FIBERS WITH A CATIONIC DYE, COMPRISING CONTACTING SAID POLYESTER FIBERS WITH A DYE BATH CONTAINING A CATIONIC DYE COMPOUND OF THE FORMULA (1),
 2. The process according to claim 1, wherein said dye bath is at a temperature of from 110* to 130*C.
 3. The process according to claim 1, wherein the dyeing is carried out in a dye bath additionally containing a non-ionic type carrier.
 4. The process according to claim 1, wherein in said compound of the Formula (I) R1 is an ethyl group, R2 is a hydrogen atom or a methyl group, R3 is an ethyl group, R4 is a hydrogen atom and R5 is a hydroxyl group or a methoxy group.
 5. The process according to claim 4, wherein said compound of the formula (I) is
 6. The process according to claim 4, wherein said compound of the Formula (I) is,
 7. The process according to claim 4, wherein said compound of the Formula (I) is,
 8. Acid-modified polyester fibers dyed by the process according to claim
 1. 